CN113549763A - Continuous production method for recovering valuable metals from battery black powder and removing organic substances - Google Patents

Abstract

The invention provides a continuous production method for recovering valuable metals from battery black powder and removing organics, which takes the battery black powder as a raw material, wherein the battery black powder contains 25-30% of nickel, cobalt and manganese, less than 2% of calcium, less than 3% of silicon dioxide, less than 3.5% of copper, 6.5% of Fe, less than 1% of aluminum and 3-5% of organics, and the method comprises the steps of leaching, removing copper, removing iron and aluminum, removing organics, controlling reaction temperature, controlling reaction PH and being assisted with a water washing process to obtain crude nickel, cobalt and manganese soluble salts without organics.

Description

Continuous production method for recovering valuable metals from battery black powder and removing organic substances

Technical Field

The invention relates to a continuous production method for recovering valuable metals from battery black powder and removing organic matters, in particular to a method for recovering valuable metals from battery black powder containing elements such as calcium, copper and iron and removing organic matters, belonging to the technical field of hydrometallurgy.

Background

The lithium ion battery has the advantages of high specific energy, long service life, high rated voltage, low self-discharge rate, light weight, strong adaptability to high and low temperature, and the like, and thus, the lithium ion battery becomes a preferred power supply for digital, communication, aviation, portable electronic products and the like. With the popularization and application of the energy storage device in power automobiles and high-power energy storage facilities, the demand of the energy storage device is explosively increased.

With the wide application of the lithium ion battery, a large amount of lithium ion batteries enter a failure and recovery stage. How to recycle the waste lithium ion battery and recycle the waste lithium ion battery as resources becomes a problem of general social attention, and valuable metals in the lithium ion battery anode material are recycled for the purposes of resource recycling and sustainable development of the industry. The generation of the lithium battery anode material waste mainly comes from the waste generated by lithium battery scrapping. Because the positive electrode material of the lithium battery contains various valuable metals such as nickel, cobalt, manganese, lithium and the like and has higher content, the valuable metals in the recovered positive electrode material of the lithium battery have plus sign economic and social benefits.

Patent CN104466294 discloses a method for recovering metals from waste nickel cobalt lithium manganate batteries, which comprises the following steps: discharging and disassembling the waste batteries or collecting the positive electrode leftover materials, roasting, dissolving in water, and filtering to obtain waste nickel cobalt lithium manganese oxide powder; mixing waste nickel cobalt lithium manganate powder and potassium bicarbonate according to a certain proportion, sintering, leaching a roasted product by using water, adding a potassium carbonate solution into the solution, filtering, supplementing carbonate, adjusting the proportion of lithium, nickel, cobalt and manganese in filter residue, ball-milling, compacting and roasting to obtain the nickel cobalt lithium manganate cathode material. The purity of the obtained product is not enough in the process of removing impurities from kerosene, and the product is difficult to reuse.

Patent 105206889a discloses a method for processing a positive electrode material of a waste nickel cobalt lithium manganate ternary battery, which comprises the following steps: pretreatment, chemical dissolution, chemical impurity removal, deep extraction impurity removal and nickel-cobalt-manganese enrichment. The method has the defect that organic matters in the anode material of the waste nickel cobalt lithium manganate ternary battery are not removed, so that when valuable metals such as nickel, cobalt and manganese are further extracted by extraction and refining, the organic matters react with an extracting agent, and the final extracting agent is invalid.

Disclosure of Invention

The invention provides a continuous production method for recovering valuable metals from battery black powder and removing the valuable metals from the battery black powder, which can effectively solve the problems.

The invention is realized by the following steps:

a continuous production method for recovering valuable metals from battery black powder and removing organic substances is characterized in that the battery black powder is used as a raw material, and the raw material comprises impurity silicon, impurity copper, impurity iron, impurity aluminum and organic substances; the method comprises the steps of leaching, copper removal, iron and aluminum removal and organic removal in sequence, wherein in each step, a rough nickel, cobalt and manganese sulfate mixed solution is obtained by controlling the reactant proportion, the reaction time, the reaction temperature and the reaction PH, and the battery black powder contains 25-30% of total nickel, cobalt and manganese, less than 2% of calcium, less than 3% of silicon dioxide, less than 3.5% of copper, 6.5% of Fe, less than 1% of aluminum and 3-5% of organic matters.

Further, the continuous production method for recovering and removing organic valuable metals from the battery black powder comprises the following steps:

putting the battery black powder and clear water into a reaction kettle, and adjusting the temperature to 60-80 ℃;

raising the reaction temperature to 70-90 ℃, and adding 98% H₂SO₄Adjusting the pH value to 1.0 for reactionFinishing;

adding sodium thiosulfate pentahydrate, keeping constant temperature reaction until the reaction is finished, and then carrying out filter pressing to obtain silicon-calcium leaching residues and a leaching solution.

Further, the continuous production method for recovering and removing organic valuable metals from the battery black powder comprises the following steps:

pumping the leaching solution into a copper removal reaction kettle, heating to adjust the temperature to 60-70 ℃, adding manganese powder, and reacting at constant temperature;

and after the reaction is finished, carrying out filter pressing to obtain the sponge copper slag and the copper-removed liquid.

Further, the continuous production method for recovering valuable metals from battery black powder and removing organic substances comprises the following steps:

pumping the copper-removed solution into a reaction kettle for removing the copper, adding 1.0-1.2 times of sodium chloride according to the measurement of the content of ferrous iron in the copper-removed solution, and keeping the temperature at 65-75 ℃ for full reaction;

and (3) adjusting the temperature to 85-90 ℃ by secondary heating, adding a soda solution until the pH value of the solution system is 4.7, fully reacting at a constant temperature, and performing filter pressing to obtain the iron-aluminite slag and the liquid after removing iron and aluminium.

Further, the continuous production method for recovering valuable metals from the battery black powder and removing the organic compounds comprises the following steps:

according to the flow ratio of 1: 0.9-1.2 pumping the liquid after iron and aluminum removal and sulfonated kerosene into an organic removal reaction device, and fully mixing until the liquid after iron and aluminum removal is clear;

and pumping the organic phase from an upper layer outlet to a rectifying tower for rectification, and pumping the liquid after iron and aluminum removal from a lower layer outlet to enter an extraction process.

Further, the continuous production method for recovering valuable metals from the battery black powder and removing organic substances comprises the following steps:

setting a fractionation point, fractionating the sulfonated kerosene and the organic matter, and separating the sulfonated kerosene and the organic matter through three-stage rectification;

and returning the rectified sulfonated kerosene to the organic removal process for use, and collecting and uniformly treating other organic matters.

The invention has the beneficial effects that: leaching, copper removal, iron and aluminum removal and organic removal are adopted. The recovery rate of valuable metal elements in the battery black powder is improved, the valuable metals in the battery black powder obtained by filter pressing are fully dissolved in the leachate in a soluble salt form through full leaching, and through a circulating water washing process, on one hand, soluble valuable metal salts are recovered and enriched by washing liquid, so that the content of the valuable metals in waste residues is effectively reduced; on the other hand, by recycling the acid leaching solution and the water washing leaching solution, waste acid generated in the production process is washed and consumed, auxiliary materials required for treating wastewater are reduced, and the wastewater treatment cost is reduced. After valuable metals are recovered, organic phases are separated and removed, so that the phenomenon that a large amount of organic matters enter an extraction refining process along with the valuable metals to enable the organic phases to react with an extracting agent to cause the failure of the extracting agent and bring huge loss is avoided. The invention has simple process, low cost and high production efficiency and is suitable for industrial large-scale production.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a process flow diagram provided by an embodiment of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.

Referring to fig. 1, a continuous production method for recovering valuable metals from battery black powder, which uses battery black powder as a raw material, wherein the raw material comprises silicon impurity, copper impurity, iron impurity, aluminum impurity and organic matter; the method comprises the steps of leaching, copper removal, iron and aluminum removal and organic removal in sequence, wherein in each step, a rough nickel, cobalt and manganese sulfate mixed solution is obtained by controlling the proportion of reactants, the reaction time, the reaction temperature and the reaction PH and being assisted by a water washing process, and the battery black powder contains 25-30% of total nickel, cobalt and manganese, less than 2% of calcium, less than 3% of silicon dioxide, less than 3.5% of copper, 6.5% of Fe, less than 1% of aluminum and 3-5% of organic matters. The production method in the scheme is a continuous production method, and by controlling a continuous process, the time can be obviously saved, the use amount of raw materials can be reduced, and the utilization rate of the raw materials can be improved.

As a further improvement, the step of leaching may be:

s11, putting the battery black powder and clean water into a reaction kettle, and adjusting the temperature to 60-80 ℃;

s12, raising the reaction temperature to 70-90 ℃, and adding 98% H₂SO₄Adjusting the pH value to 1.0 until the reaction is finished;

and S13, adding sodium thiosulfate pentahydrate, keeping constant temperature reaction until the reaction is finished, and performing filter pressing to obtain calcium silicon leaching residues and a leaching solution.

In the leaching step, the main purpose is to fully dissolve the battery black powder and then precipitate silicon and calcium impurities. In step S12, the reaction temperature is preferably 78 to 82 ℃, and the reaction time is preferably 1 to 3 hours. In one embodiment, the reaction temperature is about 80 ℃ and the reaction time is about 2 hours. It can be understood that the battery black powder can be sufficiently dissolved by controlling the reaction time and temperature.

In step S13, the reaction temperature is preferably 78 to 82 ℃, and the reaction time is preferably 1 to 3 hours. In one embodiment, the reaction temperature is about 80 ℃ and the reaction time is about 2 hours. It is understood that the calcium silicate can be sufficiently precipitated by controlling the reaction time and temperature.

In other embodiments, as a further improvement, the method further comprises a step of washing the leaching residue of calcium silicate, which comprises:

s14, washing the calcium silicon leaching residue for the first time to obtain washed calcium silicon leaching residue and washed water of the calcium silicon leaching residue;

s15, washing the first-washing calcium-silicon leaching residue with second-washing calcium-silicon leaching residue to obtain second-washing calcium-silicon leaching residue and second-washing calcium-silicon leaching residue washing water;

and S16, washing the secondary silicon-calcium leaching residue for three times to obtain a tertiary silicon-calcium leaching residue and tertiary silicon-calcium leaching residue washing water.

The step of washing the silicon-calcium leaching slag aims at avoiding the phenomenon that solution residue and slag wrapping cause loss of content of nickel-cobalt-manganese valuable metal elements in the filter pressing process in the step S13, washing the nickel-cobalt-manganese valuable metal elements in the solution residue or slag wrapping to the slag washing water through washing the silicon-calcium leaching slag, repeatedly washing and pumping the slag washing water into the water washing process for final recovery, and improving the content of the nickel-cobalt-manganese valuable metal elementsRecovering the water and reducing the consumption of water and other raw materials. 6500Kg of black powder for battery, 10m³Clear water is taken as an example; when used for the second time, can save 0.5m³The clear water is used in the right and left directions, and H₂SO₄The usage amount of the sodium thiosulfate pentahydrate can be approximately 8 percent.

In other embodiments, as a further improvement, the step of washing the leaching residue of calcium silicate further comprises;

s17, mixing the primary calcium silicon leaching residue washing water and the clear water, and putting the mixture into a reaction kettle pump to leach the battery black powder;

s18, pumping the secondary calcium silicon leaching residue washing water into the primary calcium silicon leaching residue washing for repeated washing;

and S19, pumping the washing water of the three-time calcium-silicon leaching residues into the washing of the two-time calcium-silicon leaching residues for repeated washing.

As a further improvement, the copper removal step is:

s21, pumping the leaching solution into a copper removal reaction kettle, heating to adjust the temperature to 60-70 ℃, adding manganese powder, and reacting at constant temperature;

and S22, after the reaction is finished, performing filter pressing to obtain the sponge copper slag and the copper-removed liquid.

In other embodiments, as a further improvement, the method further comprises a step of washing the sponge copper slag, which comprises:

s23, carrying out primary sponge copper slag washing on the sponge copper slag to obtain primary sponge copper slag washing and primary sponge copper slag washing water;

and S24, carrying out secondary sponge copper slag washing on the first-washing sponge copper slag to obtain second-washing sponge copper slag and secondary sponge copper slag washing water.

In other embodiments, as a further improvement, the step of washing the sponge copper slag further comprises:

s25, pumping the primary sponge copper slag washing water into the copper removal reaction kettle to be mixed with the leaching solution for repeated copper removal;

and S26, pumping the secondary sponge copper slag washing water into the primary sponge copper slag washing for repeated washing.

The copper removing step aims at removing a small amount of impurity copper in the leaching solution, the main component of the impurity copper is copper sulfate, and the manganese powder with low cost is used for replacing simple substance copper, so that the waste of copper resources is avoided, and the comprehensive utilization of the resources is improved.

As a further improvement, the iron and aluminum removing step is as follows:

s31, pumping the copper-removed liquid into a reaction kettle for removing the copper, adding 1.0-1.2 times of sodium chloride according to the measurement of the content of ferrous iron in the copper-removed liquid, and keeping the temperature at 65-75 ℃ for full reaction;

and S32, heating for the second time to 85-90 ℃, adding a soda solution until the pH value of the solution system is 4.7, carrying out full reaction at constant temperature, and carrying out filter pressing to obtain the iron-aluminite slag and the solution after iron and aluminum removal.

In other embodiments, as a further improvement, the method further comprises a step of washing the iron aluminous slag, which comprises:

s33, carrying out primary washing on the iron-alumen-based slag to obtain a washed iron-alumen-based slag and primary washing water of the iron-alumen-based slag;

s34, washing the first iron washing alumen residue with secondary iron alumen residue to obtain second iron washing alumen residue and secondary iron alumen residue washing water; and

s35, washing the second iron washing alumite slag for three times to obtain third iron washing alumite slag and third iron washing alumite slag washing water.

In other embodiments, as a further improvement, the step of washing the iron alum slag further includes:

s36, pumping the primary iron-aluminite slag washing water into the iron and aluminum removing reaction kettle to be mixed with the copper-removed liquid to repeatedly remove iron and aluminum;

s37, pumping the secondary iron alum slag washing water into the primary iron alum slag washing for repeated washing;

and S38, pumping the tertiary iron alum slag washing water into the secondary iron alum slag washing for repeated washing.

In the step of removing the iron and the aluminum, the iron and the aluminum elements are mainly separated from the liquid after the copper removal in the form of iron-alumen-based slag sediment, in order to avoid oxidation reaction between other metal impurities and the sodium chlorate in the liquid after the copper removal, 1.0-1.2 times of the sodium chlorate in excess is added, so that bivalent iron elements in the liquid after the copper removal are just completely oxidized into ferric iron, and the ferric iron, the aluminum elements in the liquid after the copper removal and the alkali react to generate the iron-alumen-based slag sediment.

In other embodiments, as a further improvement, the continuous production method for recovering and removing organic from the battery black powder comprises the following steps:

s41, according to the flow ratio of 1: 0.9-1.2 pumping the liquid after iron and aluminum removal and sulfonated kerosene into an organic removal reaction device, and fully mixing until the liquid after iron and aluminum removal is clear;

s42, pumping the organic phase from the upper layer outlet to a rectifying tower for rectification, and pumping the liquid after iron and aluminum removal from the lower layer outlet to obtain a nickel-cobalt-manganese sulfate mixed solution.

In the step of removing the organic matter, in order to fully mix the liquid after removing the iron and the aluminum with the sulfonated kerosene, the characteristic that the mass of the sulfonated kerosene is lighter than that of the liquid after removing the iron and the aluminum is utilized, and the mixing ratio is 1: and pumping the liquid after iron and aluminum removal from an upper inlet of the organic removal device at a flow rate of 0.9-1.2, pumping sulfonated kerosene from a lower inlet of the organic removal device, allowing the sulfonated kerosene to pass through the middle of the liquid after iron and aluminum removal, floating the sulfonated kerosene with the organic phase on an upper layer of the liquid after iron removal, overflowing the sulfonated kerosene from an overflow outlet, and pumping the sulfonated kerosene from an upper outlet to a rectifying tower for rectification. For thorough mixing, it is preferred that the flow ratio in the early stage is 1: 0.9, pumping the liquid after iron and aluminum removal and sulfonated kerosene into an organic removal reaction device, and then gradually increasing the flow rate of the sulfonated kerosene according to the flow rate ratio of 1:1.2 pumping the liquid after iron and aluminum removal and sulfonated kerosene into a reaction device for removing organic matters. Therefore, on one hand, the usage amount of the sulfonated kerosene can be reduced, and on the other hand, the mixed replacement time can be saved. If the flow rate is low (0.9 sulfonated kerosene is pumped into the organic removal reaction device), the mixing time is prolonged with the increase of the addition amount. If the high flow rate (1.2 sulfonated kerosene is pumped into the organic removing reaction device) is directly adopted, the use amount of the sulfonated kerosene is obviously increased.

Further, the continuous production method for recovering valuable metals from the battery black powder and removing organic substances comprises the following steps:

setting a fractionation point, fractionating the sulfonated kerosene and the organic matter, and separating the sulfonated kerosene and the organic matter through three-stage rectification;

and returning the rectified sulfonated kerosene to the organic removal process for use, and collecting and uniformly treating other organic matters.

And recovering the organic removed iron and aluminum liquid to obtain a rough mixed solution of nickel, cobalt and manganese sulfate, thereby realizing the recovery of valuable metal elements.

Example 1: production raw materials: the battery black powder (the content ratio is 29 percent of nickel, cobalt and manganese, 0.5 percent of Ca and SiO)₂2.6 percent of 6500Kg, 1.6 percent of Cu, 1.5 percent of Fe, 0.8 percent of Al and 3 to 5 percent of organic matter, and 98 percent of H₂SO₄600Kg of sodium thiosulfate pentahydrate, 150Kg of manganese powder/iron powder, 80Kg of sodium chlorate, 400Kg of soda ash and sulfonated kerosene.

Production and preparation:

(1) preparing silicon-calcium leaching residues: (i) feeding: to 40m³The reaction kettle is supplemented with 10m³Clear water, heating to adjust the temperature to 70 ℃, and keeping the temperature for 1.0 hour. (ii) Keeping the constant temperature of 80 ℃, adding 98% H₂SO₄The pH was adjusted to 1.0 and the reaction was carried out for 2.0 hours. (iii) 600Kg of sodium thiosulfate pentahydrate was added and the reaction was carried out at a constant temperature of 80 ℃ for 2.0 hours. (iv) pumping into a pressure filter for pressure filtration of 200 square meters to obtain the calcium silicon leaching residues and the leaching solution.

(2) Washing the leached residue of calcium silicate: (i) primary washing: to 12m³The slurrying kettle is supplemented with 8.0m³Washing the silicon-calcium leaching residue, unloading the silicon-calcium leaching residue into a slurrying kettle, heating to adjust the temperature to 60 ℃, stirring at constant temperature for 2.0 hours, and pumping into a pressure filter of square meter 200 for pressure filtration to obtain the silicon-calcium leaching residue. (ii) And (3) secondary washing: to 12m³The slurry kettle is supplemented with 7.2m³Washing the calcium silicon leaching residue with water, discharging the calcium silicon leaching residue into a slurrying kettle, heating to 60 deg.C, and keeping the temperature constantStirring for 1.5 hours at a warm temperature, and then performing pressure filtration by using a pressure filter of 200 square meters to obtain the leaching residue of the calcium silicon dioxide. (iii) And (3) washing for three times: to 12m³The slurry kettle is supplemented with 6.0m³And (3) clear water, discharging the calcium silicon leaching residue from the second washing into a slurrying kettle, heating to adjust the temperature to 60 ℃, stirring at constant temperature for 1.5 hours, and then performing pressure filtration by using a pressure filter of 200 square meters and maintaining the pressure for 2 hours to obtain the calcium silicon leaching residue from the third washing.

(3) Copper removal: (i) pumping 30m into a copper removal reaction kettle³Heating the leachate to 65 ℃, adding 130Kg of manganese powder, and reacting at constant temperature for 1.0 hour. (iii) Pumping into a pressure filter of 200 square meters for pressure filtration to obtain the sponge copper slag and the liquid after copper removal.

(4) Washing the sponge copper slag: (i) primary washing: to 12m³The slurrying kettle is supplemented with 8m³Washing sponge copper slag with washing water for two times, adjusting the temperature to 60 ℃, and adding 0.3m³And (3) stirring the sulfuric acid or the hydrochloric acid at constant temperature for 1.5 hours, and pumping the mixture into a pressure filter for pressure filtration of a 200 square meter to obtain the sponge copper washing residue. (ii) And (3) secondary washing: to 12m³Adding 6.0 parts of clear water into the slurrying kettle, adjusting the temperature to 60 ℃, stirring at constant temperature for 1.0 hour, pumping into a pressure filter of 200 square meters for pressure filtration, and maintaining the pressure for 2 hours to obtain the second-washing sponge copper slag.

(5) Removing iron and aluminum: (i) pumping 28m into a reaction kettle for removing the aluminum³And (3) removing copper, performing second-order iron content detection on the solution after copper removal, heating to adjust the temperature to 70 ℃, adding 1.0-1.2 times of sodium chloride according to the theoretical calculation amount of the divalent iron content, and reacting at constant temperature for 1.0 hour. (iii) Heating for the second time to 88 deg.C at 0.6m³Adding the sodium carbonate solution at the flow rate of/h until the pH value of the solution system is 4.7, and reacting for 1.0 hour at constant temperature. (iv) pumping into a pressure filter for pressure filtration of 200 square meters to obtain iron-aluminum-vanadium slag and the solution after iron and aluminum removal (namely the crude nickel-cobalt-manganese sulfate mixed solution).

(6) Washing the iron aluminous slag: (i) primary washing: adding 8.0m into the primary washing and pulping kettle³And (2) washing the iron aluminous slag, discharging the iron aluminous slag into a slurrying kettle, adjusting the temperature to 70 ℃, adding a sulfuric acid solution until the pH value of a solution system is 2.2, stirring at constant temperature for 3.0 hours, and pumping into a filter press with the square meter of 200 for filter pressing to obtain the iron aluminous slag. (ii) And (3) secondary washing: 8.0m is added into the secondary washing slurrying kettle³Washing water of three-washing iron-alumen-oxide slag and adjusting temperatureStirring at the constant temperature of 70 ℃ for 2.0 hours, and pumping into a pressure filter for pressure filtration of 200 square meters to obtain the iron-aluminum-alum-washed residue. (iii) And (3) washing for three times: 8.0m is added into the secondary washing slurrying kettle³And (3) adjusting the temperature of clear water to 70 ℃, stirring for 1.5 hours at constant temperature, and pumping into a pressure filter of 200 square meters for pressure filtration to obtain the iron-aluminum-vanadium trisilicate residue.

(7) Removing organic matters: according to the following steps: pumping the liquid after removing the iron and the aluminum and the sulfonated kerosene into an organic removing device at a flow rate of 0.9, gradually increasing the amount of the sulfonated kerosene to 1:1.2, pumping the liquid after removing the iron and the aluminum and the sulfonated kerosene into the organic removing device, according to the principle of similar phase dissolution, preferentially pumping the organic phase in the leachate into the sulfonated kerosene for mixing and clarification, realizing separation of an oil phase and a water phase, pumping the organic phase from an outlet of an upper layer to a rectifying tower, and pumping the leachate out from an outlet of a lower layer to obtain a nickel-cobalt-manganese sulfate mixed solution. And (3) rectifying, namely, enabling the sulfonated kerosene to enter a rectifying tower, and separating the sulfonated kerosene from organic matters in the battery through three-stage rectification according to different fractionation points of the organic matters in the sulfonated kerosene and the black powder. The sulfonated kerosene obtained by rectification is returned to the organic working procedure for use, and other organic materials are collected and treated uniformly.

The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (6)

1. A continuous production method for recovering valuable metals from battery black powder and removing organic substances is characterized in that the battery black powder is used as a raw material, and the raw material comprises impurity silicon, impurity copper, impurity iron, impurity aluminum and organic substances; the method comprises the steps of leaching, copper removal, iron and aluminum removal and organic removal in sequence, wherein in each step, a rough nickel, cobalt and manganese sulfate mixed solution is obtained by controlling the reactant proportion, the reaction time, the reaction temperature and the reaction PH, and the battery black powder contains 25-30% of total nickel, cobalt and manganese, less than 2% of calcium, less than 3% of silicon dioxide, less than 3.5% of copper, 6.5% of Fe, less than 1% of aluminum and 3-5% of organic matters.

2. The continuous production method for recovering and removing organic valuable metals from battery black powder according to claim 1, wherein the leaching step comprises:

putting the battery black powder and clear water into a reaction kettle, and adjusting the temperature to 60-80 ℃;

raising the reaction temperature to 70-90 ℃, and adding 98% H₂SO₄Adjusting the pH value to 1.0, and finishing the reaction;

adding sodium thiosulfate pentahydrate, keeping constant temperature reaction until the reaction is finished, and then carrying out filter pressing to obtain silicon-calcium leaching residues and a leaching solution.

3. The continuous production method for recovering and removing organic valuable metals from battery black powder according to claim 2, wherein the step of removing copper comprises:

pumping the leaching solution into a copper removal reaction kettle, heating to adjust the temperature to 60-70 ℃, adding manganese powder, and reacting at constant temperature;

and after the reaction is finished, carrying out filter pressing to obtain the sponge copper slag and the copper-removed liquid.

4. The continuous production method for recovering and removing organic valuable metals from battery black powder according to claim 3, wherein the iron and aluminum removing step comprises:

pumping the copper-removed solution into a reaction kettle for removing the copper, adding 1.0-1.2 times of sodium chloride according to the measurement of the content of ferrous iron in the copper-removed solution, and keeping the temperature at 65-75 ℃ for full reaction;

and (3) adjusting the temperature to 85-90 ℃ by secondary heating, adding a soda solution until the pH value of the solution system is 4.7, fully reacting at a constant temperature, and performing filter pressing to obtain the iron-aluminite slag and the liquid after removing iron and aluminium.

5. The continuous production method for recovering and removing organic valuable metals from battery black powder as claimed in claim 4, wherein the step of removing organic is:

according to the flow ratio of 1: 0.9-1.2 pumping the liquid after iron and aluminum removal and sulfonated kerosene into an organic removal reaction device, and fully mixing until the liquid after iron and aluminum removal is clear;

and pumping the organic phase from an upper layer outlet to a rectifying tower for rectification, and pumping the iron and aluminum removed liquid from a lower layer outlet to obtain a nickel-cobalt-manganese sulfate mixed solution.

6. The continuous production method for recovering and removing organic valuable metals from battery black powder according to claim 5, wherein the rectification comprises the following steps:

setting a fractionation point, fractionating the sulfonated kerosene and the organic matter, and separating the sulfonated kerosene and the organic matter through three-stage rectification;

and returning the rectified sulfonated kerosene to the organic removal process for use, and collecting and uniformly treating other organic matters.

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